DE2357102A1 - PHOTOGRAPHIC MATERIAL CONTAINS A MAGENTA COUPLER - Google Patents

Description

To you.;.-·;;. ■ ". -._- ,." ■! I-'ckfir Dr.- ¹ - ; ''... ■ · * .-, lay

Dt .-; ng. \ · - ': · ■. :: ■; nar ^ November 15, 1973

Munich 27, Maxnn'nurs': Λ?

P 7421

Pugi Photo Film Co., Ltd.

No. 210, Nakanuma, Minami Ashigara-shi,

Kanagawa, Japan

Photographic material containing a Maqenta coupler

The invention relates to a silver halide photographic emulsion and their use. In particular, the invention relates to one containing at least one magenta coupler silver halide photographic emulsion.

It is known that during the exposure and subsequent development of color photographic silver halide material Due to indophenols, indanilines, indamines, azomethines, phenoxazines, phenazines and similar dyes the reaction of the oxidation products of the primary aromatic Amines and couplers are formed which lead to the formation of the color images. As a rule, a subtraction process is used for color reproduction.

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Color images in the colors yellow, magenta and cyan are formed, which are the complementary colors to blue, green or are red. Acylacetamide or dibenzoylmethane or their derivatives are used to produce the yellow images Coupler used. To form the magenta images, couplers of the pyrazolone, cyanoacetyl or indazolone type are used used. Phenol-type couplers such as phenols are used to produce the cyan images or naphthols.

In these color photographic processes, the couplers required to form the colors are either the developer to be used or already the light-sensitive one photographic emulsion layer added. The reaction between the oxidation products of the Developing the latent images formed color-developing Substances with the couplers enter during development.

For the generation of the magenta images in the color photographic processes based on three basic colors a number of 2-pyrazol-5-one derivatives are known. As a substituent in the 3-position of the pyrazol-5-one ring are, for example, alkoxy groups (US Pat. No. 2,439,098), acylamino groups (US-PS 2,369,439 and 2,600,788) and a urea group (US-PS 3,558,319) and an alkyl group, an aryl group and an anilino group are known. Since the issue of U.S. Patent 2,311,081 (Reissue 22,329), the 3-anilino-pyrazol-5-one couplers have been described many times and a number of improvements have been proposed. In this context, it has been described in GB-PS 956 261 that azomethine dyes, which are obtained from such derivatives were obtained whose ortho division to the anilino group are substituted with alkoxy or halogen, in particular an advantageous spectral for such color images Show absorption curve by making a particularly narrow

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Have absorption of the undesired area in the area of red light. Non-diffusing couplers that too of this type of coupler and which can be incorporated directly into the photographic emulsions are those known 3- (acylaminoanilino) -2-pyrazol-5-ones of the general formula:

D ₅ CONH

Cm

where D. aryl, ^D 2 ^CO "" ^Ac yl » ^D o hydrogen or a coupling-off group which is removed by the oxidation product of a primary aromatic amine developer, for example a phenoxy group, and L is chlorine or methoxy.

If these couplers are already used in the preparation of the photographic materials in the silver halide photographic emulsion are added, they must not diffuse, since if they diffuse into the uncontrolled adjacent emulsion layers with different spectral sensitivities would produce mixing effects that would impair a true-to-color reproduction. For this reason it is necessary to use the coupler molecule with a hydrophobic group with 8 or more carbon 7 to provide atoms as a ballast group. With such ballast groups, the diffusivity of the coupler can be felt be reduced.

For incorporating non-diffusing couplers into photographic

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See emulsion layers are essentially three types of process known:

(1) The aqueous system: couplers with groups that increase water solubility promote, for example with carboxyl groups or sulfonic acid groups, are in aqueous alkaline Media dissolved and added to the emulsion in the form of a neutral or alkaline aqueous solution, the Emulsion is then neutralized with an acid,

(2) The oil system: a coupler is made in an organic solvent solved. The organic solution thus obtained is emulsified and dispersed colloidally in an aqueous medium, the dispersion thus obtained is then added to the photographic emulsion.

(3) The coupler is heated and melted, the melted coupler then either being added directly to the emulsion or is dispersed in an aqueous medium.

One of them for making green sensitive photographic prints Emulsion layers suitable magenta coupler, to be incorporated by the oil process, the following properties are expected: (1) The couplers should have a high coupling reactivity with the oxidation products of the developer; (2) the color development Magenta images produced by winding should have appropriate optical absorption characteristics in view of the Subtraction methods working with the three primary colors exhibit; (3) The magenta images must be time-stable and are allowed to stand up even under unusual storage conditions Don `t change; (4) the couplers must not adversely affect the photographic emulsions; and (5) the couplers should be in organic solvents for the sake of ease

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Dispersibility should be easily soluble and should be at the same time Practically does not crystallize from organic solvents.

The previously known magenta couplers for the oil system show inadequate coupling reactivity, especially when it is dispersed in an emulsion layer are. It was therefore difficult to use the oil method to incorporate green-sensitive emulsion layers to produce high quality photographic properties.

The magenta images of the subtractive with three. Primary colors working color photographic process absorb precisely in the wavelength range of maximum brightness, so that their optical absorption characteristics match the color quality obtained by parreproduction processes Color images influenced quite significantly «So» it was assumed that one could improve the steepness of the spectral Absorption curve and a decrease in the specific secondary absorption of the pyrazolone type magenta couplers Could obtain magenta images with good absorption characteristics. A number of attempts are already in this Direction has been carried out.

However, the color images obtained using most of the conventional magenta couplers tend to be delicate. Changes in color when stored at higher temperatures and higher humidity for long periods of time. In order to suppress such color changes, formalin had to be added during development.

The invention is therefore based on the problem of the disadvantages the known color photographic emulsions containing a magenta coupler and emulsions thereof

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To create kind that can be produced using new magenta couplers using the oil system and can be used for the construction of color photographic material with excellent and precisely toned color reproduction according to the subtraction process, whereby the magenta images are stored for a long time even under the most difficult and unusual storage conditions without impairing the color quality can be. This good shelf life should be made possible without the use of formaldehyde or similar substances as stabilizers during development. The magenta couplers to be used should be easy to manufacture from easily available materials.

To solve this problem, according to the invention, a proposed silver halide photographic emulsion of the type mentioned, which is characterized by the presence at least one non-diffusing magenta coupler of the 3-anilino-2-pyrazol-5-one type, the phenyl ring of which is in at least one of the two ortho divisions with a halogen atom, Alkyl, aryl, alkoxy, aryloxy, alkylthio, arylthio, Amino, amido, hydroxyl, cyano or nitro and in at least one of the meta positions or the para position with one Alkoxycarbony! Group is substituted.

The 4-position of these 2-pyrazol-5-one derivatives can by a radical which is removed by an oxidation product of the primary aromatic amine developer can be.

The main advantage of the magenta couplers used for the proposed silver halide emulsions is to be found in that they enable the emulsions to be produced according to the oil system described above. The under Color photographic produced using these emulsions

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Materials enable an extremely true color Reproduction.

Preferred examples of couplers according to the invention include Compounds falling under the general formula below,

—NH-C-

CH -Z

= O

(D.

in which R 1 is an ary group whose rings can be substituted with any of the groups also used in the coupler, for example with halogen, cyano, nitro, hydroxyl, carboxyl, amino (for example amino, N-alkylamino, N, N- Dialkylamino, N-arylamino, N-alkyl-N-aryl-amino), carboxylic acid ester group (e.g. carbomethoxy, carboathoxy, carbphenoxy), a sulfo group, a sulfoester (e.g. methoxysulfonyl, butoxysulfonyl, phenoxysulfonyl), an amido group (e.g. (a- (2,4-di-tert-Amylphenoxy) -acetamido) -benzamido, a- (3-Pentadscylphenoxy) -butyramido, a- (4-tert-Butylphenoxy) -propionamido, 3,5-dicarboxybenzamido, ethylsulfonamido , Phenylsulfoamido), a carbamyl group (e.g. N-methylcarbamyl, N-phenylcarbamyl), a sulfamyl group (e.g. N-propylsulfamyl, N-tolylsulfamyl), an alkoxy group (e.g. methoxy, butoxy), an aryloxy group (e.g. phenoxy, tolyloxy, naphthoxy).

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is for example one of the following compounds, namely phenyl, 2-chlorophenyl, 4-chlorophenyl, 2,5-dichlorophenyl, 2,6-dichlorophenyl, 2,4,6-trichlorophenyl, 2-bromophenyl, 3,5-dibromophenyl, 2 -Cyanophenyl, 4-cyanophenyl, 3-nitrophenyl, 4-nitrophenyl, 4-methylphenyl, 2,6-dimethylphenyl, 2,6-diethylphenyl, 4-butylphenyl, 2-trifluoromethylphenyl, 2-ethoxyphenyl, 4-phenylphenyl, 4 -Phenoxyphenyl, N-methylbenzamidophenyl, N, N-diphenylcarbamylphenyl, N, N-diphenylsulfamylphenyl, Ν, Ν-dibutylsulfamylphenyl, phenyl-N-methyl-sulfo> -namidophenyl, 2-methyl-5-nitrophenyl, 2-chloro-5- cyanophenyl, 5-chloro-2-methylphenyl, 2,6-dichloro-4-methylplienyl, 2,4-dichloro-6-methylphenyl, 2-chloro-4,6-diraethylphenyl, 2,6-dichloro-4 -methoxyphenyl, 2,6-dichloro-4-nitrophenyl, 2,4,6-triinethyl-3-nitrophenyl, 2,4,6-trimethyl-3-substituted aminophenyl, 2,6-dichloro-4-methoxycarbonylphenyl, 2, 6-dichloro-4-benzyloxycarbonylphenyl or 2,6-dichloro-4-carboxyphenyl, or in which R is also a heterocyclic G is group, for example a radical of a five-membered or six-membered heterocyclic compound, such as 2-thiazolyl, 2-benzothiazolyl, 2-benzoxazolyl, 2-oxazolyl, 2-imidazolyl or 2-benzimidazolyl, and in which R _? is a straight or branched alkyl group having 1-32 carbon atoms or a cycloalkyl group (e.g. cyclohexyl or terpenyl); the alkyl group can optionally be substituted with halogen, nitro, hydroxyl, carboxyl, an amino group (for example an unsubstituted amino group, an alkylamino group, a dialkylamino group, an anilino group or an N-alkylanilino group), an aryl group, a carboxyester group (for example carboalkoxy group, carboaryloxyl group) , an amido group (for example acetamido, butylamido, ethylsulfonamido, N-methylbenzamido, N-propylbenzamido, 4-tert-butylbenzamido or diacylamido), a carbamyl group (for example unsubstituted carbamyl, N-octadecylcarbamyl, N-octadecylcarbamyl, 3Sr-methyl, N-N-methyl -phenyl-carbaityl or

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3-pentadecylphenylcarbamyl), a sulfamyl group (for example N-propylsulfamyl, N-tolylsulfamyl), an alkoxy group (e.g. ethoxy, octadecyloxy), an aryloxy group (for example phenoxy, tolyloxy, naphthyloxy), a sulfonic acid group, a sulfonyl group (for example Methylsulfonyl, octadecylsulfonyl, ethoxysulfonyl, Decyloxysulfonyl, phenylsulfonyl, tolylsulfonyl, phenoxysulfonyl) or other

and in which X and Y each have one of the following meanings have: alkyl (e.g. methyl, tert-butyl, octyl, dodecyl), aryl (e.g. phenyl, tolyl), Alkoxy (e.g. methoxy, octyloxy), aryloxy (e.g. Phenoxy, p-tert-butylphenoxy, naphthoxy), alkylthio (for example methylthio, octylthio), arylthio (for example phenylthio), an amino group (for example an unsubstituted amino group or methylamino, Diethylamino, anilino), an amido group (for example acetamido, butylamido, methylsulfonamido, diacylamido), Halogen (for example fluorine, chlorine, bromine), hydroxyl, cyano or nitro, where Y can also be hydrogen! and in which Z denotes hydrogen or a radical which can be removed by coupling, for example one of the following groups: thiocyano, acyloxy (e.g. acetoxy, dodecanoyloxy, octadecanoyloxy, 3-n-pentadecylphenoxyacetoxy, Benzoyloxy, β-naphthoyloxy, 3- (4- (2,4-di-tertpentylphenoxy) butylamido) benzoyloxy or similar groups), aryloxy (for example phenoxy, p-chlorophenoxy, p-nitrophenoxy, Naphthoxy), halogen (e.g. chlorine or Fluorine), arylazo (for example substituted or unsubstituted phenylazo or naphthylazo), 2-aryltriazolyl (for example 2-benzotriazolyl, 2-naphthotriazolyl), Alkylthio (for example with 4 - 10 carbon atoms in Allcylresc), Arylthio (for example Phenylbhio, IrTaplitliy-l one heterothio group (for example 2-benzothiazolylthio,

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l-phenyl-5-tetrazdlylthio, 2-benzoxazolylthio, 2-benzimidazolylthio, 5-phenyl-1,3,4-oxadiazolyl-2-thio), a cycloalkyl thio group (for example a cyclohexylthio group) or a cycloalkoxy group (e.g. a cyclohexyloxy group).

In particular, groups of the following general formula are preferred for the radical R 1:

in which U, denotes a halogen atom, an alkyl group, an alkoxy group, an alkyl thio group, an aryl group, a Aryloxy group, an aryltliio group or a cyano group; in which U- is a hydrogen atom, a halogen atom, a Alkyl group, an alkoxy group, an alkyl thio group, an aryl group, an aryloxy group, an aryl thio group or a cyano group; and in the further U_, U ^, and Ujje a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an alkyl thio group, an aryl group, an aryloxy group, an aryl thio group, a cyano group, an acylamino group, a carbamyl group, a urea group, a sulfonamido group, a sulfamyl group, a Alkylsulfonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, represent an aralkoxycarbonyl group, a carboxy group or an arylcarbonyl group.

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The molecule of the magenta coupler represented by the above general formula (I) preferably contains at least a hydrophobic group with 8-32 carbon atoms as a basic group. This hydrophobic group makes the Coupler easily soluble in organic solvents. the Coupler solution is therefore easily dispersible in a hydrophilic colloid. The coupler will crystallize out also avoided in this way, whereby a stabilized photographic material is obtained. If the Number of carbon atoms in the hydrophobic group is less than 8, the coupler will dissolve in the treatment baths, for example in the developer bath and begins in the photographic Diffuse material, which affects the color accuracy of the images. If on the other hand the number the carbon atoms of the ballast group are more than 32, decreases the mutual interaction between the coupler molecules in such a way that such couplers are already extremely difficult in organic solvents become soluble. It is therefore not recommended to use couplers whose ballast groups are less than 8 or more contain than 32 carbon atoms.

As typical representatives for such hydrophobic ballast groups the following may be mentioned as examples: alkyl groups, alkoxyalkyl groups, alkenyl groups, substituted with alkyl groups Aryl groups, aryl groups substituted with alkoxy groups, or terphenyl groups. These hydrophobic groups can, for example, be substituted with one of the following groups be: halogen, for example fluorine or chlorine, nitro, cyano, alkoxycarbonyl, amido, carbamyl, sulfonamido, or others. Below are some specific examples of these hydrophobic groups: n-octyl, 2-ethylhexyl, tert-octyl, n-nonyl, n-decyl, n-dodecyl, 1,1-dimethyldecyl, 2,2-dimethyldecyl, n-octadecyl, 2- (n-hexyl) -decyl, n-octadecyl, 9, IO-dichloroctadecyl, heptyloxyethyl, 2,4-di-tert-pentyl-

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cyclohexyldodecyloxypropyl, oleyl, 2,4-di-tert-butylphenyl, 2,4-di-tert-pentylphenyl, 2,4-di-tert-pentyl-6-chlorophenyl, 3-n-pentadecylphenyl , 2-dodecyloxyphenyl, 3- Heptadecyloxyphenyl, O-terphenyl or perfluoroheptyl.

These hydrophobic radicals are contained in at least one of the radicals R ₁ , R 2, X, Y or Z in the general formula (I). The hydrophobic radicals of the type described can either themselves form one of the radicals R _{1 , R 2} , X 1 Y or Z or in combination with other aliphatic or aromatic or heterocyclic groups, the hydrophobic groups mentioned being attached directly to these combination groups or via a divalent group Are bridged, for example via an ether bond, a thioether bond, an amido bond, a ureido bond, a sulfonamido bond, a carbonyl bond, an oxycarbonyl bond or an amino bond.

Couplers which contain strongly hydrophilic groups in the radicals R ₁ , R ₃ , X, Y or Z of the formula (I), for example a carboxyl group, a sulfonic acid group or a sulfonoxy group, can also be added to the photographic emulsions by the aqueous process, ie in aqueous solution.

Of the couplers which come under the aforementioned general formula (i), those in which the substituent R _{1 is} a phenyl group with a radical substituted in at least one of the ortho positions with alkyl, alkoxy or alkylthio, or a halogen atom or a cyano group as a substituent has excellent heat resistance and light resistance. Those couplers in which R _{2 is} unsubstituted alkyl or an alkyl group substituted with alkoxy, aryloxy, acyloxy, alkoxycarbonyl, acylamino, carbamyl, or one

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Similar group, the number of carbon atoms of the substituent R_ in the range of 8-32, can be synthesized in a simple manner. Those couplers of the general formula (I) in which X is a halogen atom, an alkoxy group having 5 or fewer carbon atoms or an aryloxy group having 12 or fewer carbon atoms are distinguished by advantageous spectral absorption characteristics of the magenta images formed. Couplers in which Y is hydrogen are distinguished above all by the fact that the starting materials for the production of these couplers are available without problems and in a large selection. In addition, the synthesis can be carried out easily in this case. Coupler of the general formula (i) in which the radical R _? OOC- is in the 5-position in the anilino group, are distinguished above all by the fact that they are easily soluble in coupler solvents.

The magenta couplers which are used in the context of the invention also include derivatives of the pyrazol-5-one compounds, which fall under the general formula (I), for example the S-anilino-S-acyloxypyrazole, which by Preparation of the pyrazol-5-one compounds with acylating agents can be obtained, and the alkylidene bispyrazolones and the arylidene-bis-pyrazolones, which are obtained by reacting the pyrazol-5-ones with aldehydes can.

Representative examples of the magenta couplers used for the silver halide photographic emulsions which can be used in accordance with the invention are as follows listed, although this list is not intended to limit the invention:

1- (2,4,6-trichlorophenyl) -2-pyrazol-5-one compounds such as ; 40S621 / 1065

for example the:

(1) 3 - ^ - dodecyloxy-S-methoxycarbonylanilino) derivatives

(2) 3- (2-chloro-5- (dodecyloxycarbonylmethoxycarbonyl) anilino) derivatives

(3) 3- (2-methyl-5-tetradecyloxycarbonylanilino) derivatives

(4) 3- (2-methoxy-5-tetradecyloxycarbonylanilino) derivatives

(5) 3 - ^ - chloro-S-tetradecyloxycarbonylanilino) derivatives

(6) 3- (2-Methylthio-5-hexadecyloxycarbonylanilino) derivative

(7) 3- (2-Methoxy-5- (2- (2,4-di-tert-pentylphenoxy) ethoxycarbonyl) anilino) derivatives

(8) 3- (2-chloro-5- (2- (2,4-di-tert-pentylphenoxy) ethoxycarbonyl) ) anilino) derivatives

(9) 3- (2-chloro-5- (2- (2-dodecylsuccinimido) ethoxycarbonyl) ) -Anilino) -derivatives

(10) 3- (2-chloro-5- (2-butoxytetradecyloxycarbonyl) anilino) -. Derivatives

(11) 3- (2-chloro-5- (3- (2,4-di-tert-pentylphenoxy) propoxycarbonyl) anilino) derivatives

(12) 3- (2 ~ methyl-5- (4- (2,4-di-tert-pentylphenoxy) butoxycarbonyl) anilino) derivatives

(13) 3- (2-chloro-5- (2- (2,4-di-tert-pentylphenoxy) butoxycarbonyl) anilino) derivatives

(14) 3- (2-chloro-5- (2- (3-pentadecylphenoxy) ethoxycarbonyl) anilino) derivatives

(15) 3- (2-Chloro-5- (2- (3-tert-butyl-4-hydroxyphenoxy) tetradecyloxycarbonyl) anilino) derivatives

(16) 3- (2-Chloro-5-dodecyloxycarbonylanilino) -4- (4-nitrophenoxy) derivatives

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(17) 3- (2-Methoxy-5-tetradecyloxycarbonylanilino) -4-acetoxy derivatives

(18) 3- (2-Methoxy-5- (2-hexyldecyloxycarbonyl) anilino) -4- (1-naphthylazo) derivatives

(19) 3- (2-Chloro-5-hexadecyloxycarbonylanilino) -4 - ((1-phenyl-5-tetrazolyl) -thio) derivatives

(20) 3- (2-chloro-5-hexadecyloxycarbonylanilino) -4- (4-methoxyphenylazo) -Derivatives "

1- (2,5-dichlorophenyl) -2-pyrazol-5-one compounds , for example the

(21) 3- {2-Chloro-4- (2-dodecyloxycarbonylethoxycarbonyl) anilino) derivatives

(22) 3- (2-chloro-5- (2- (2,4-di-tert-pentylphenoxy) ethoxycarbonyl) anilino) derivatives.

1- (2 ^ -Dichlor-G-methylphenyl) -2-pyrazol-5-one compounds, for example the

(-23) 3- (2-Methoxy-5-dodecyloxycarbonylanilino) derivatives

(24) 3- (2-Chloro-5-dodecyloxycarbonylanilino) derivatives.

1- (2,6-dichloro-4-methylphenyl) -2-pyrazol-5-one compounds, such as the

(25) 3- (2-Methoxy-5- (tetradecyloxycarbonylmethoxycarbonyl) anilino) derivatives

(26) 3- (2-Chloro-5- (2-hexyldecyloxycarbonyl) anilino) derivatives.

1- (2,6-Diclilor-4-ynethoxyphenyl) -2-pyrazol-5-one compounds, for example the

4 0 9 ^: 8 2 ti / 1 Q 6 p

(27) 3- (2-Chloro-4-tetradecyloxycarbonylanilino) derivatives

(28) 3- (2-chloro-5-tetradecyloxycarbonylanilino) derivatives.

1- (2-chloro-4,6-dimethylphenyl) -2-pyrazol-5-one compounds, for example the

(29) 3- (2-Acetamido-5-octyloxycarbonylanilino) derivatives

(30) 3- (2-chloro-5- (2- (2,4-di-tert-pentylphenoxy) ethoxycarbonyl) anilino) derivatives.

1- (2,6-dichloro-4- (4- (2,4-di-tert-pentylphenoxy) -butylamido) -phenyl) -2-pyrazol-5-one compounds, such as the

(31) 3- (2-Chloro-4-methoxycarbonylanilino) derivatives

(32) 3- (2-Methoxy-5-ethoxycarbonylanilino) derivatives.

1- (4- (2- (2,4-di-tert-pentylphenoxy) -butylamido) -phenyl) -2-pyrazol-5-one compounds, such as the

(33) β- (2-Chloro-5-methoxycarbonylanilino) derivatives

(34) 3- (2-Chloro-5-methoxycarbonylanilino) -4-phenylthio derivatives.

Other 2-pyrazol-5-one compounds such as

(35) 1- (2-Chlorophenyl) -3- (2-phenoxy-S-dodecyloxycarbonylanilino) derivatives

(36) 1- (4-Chlorophenyl) -3- (2-chloro-5- (2- (4-tert-butylphenoxy) tetradecyloxycarbonyl) anilino derivatives

(3.7) 1- (2,4, e-Trimethyl-3- (2- (3-pentadecylphenoxy) butylamido) phenyl ) -3- (2-chloro-5-a'thoxycarbonylanilino) · derivatives

ÜÖ9821 / 106S

(38) 1- (4- (4-tert-butylphenoxy) phenyl (3- (2-chloro-5-dodecyloxycarbamoylanilino)) -4- (3-butylcarbamoylphenyl) thio) derivatives

(39) 1- (2,6-Dichloro-4-methoxycarbonylphenyl) -3- (2-chloro-5-tetradecyloxycarbonylanilino) derivatives

(40) 1- (2,6-Dichloro-4-benzyloxycarbonylphenyl) -3- (2-chloro-5-hexadecyloxycarbonylanilino) derivatives

(41) 1- (2,6-Dichloro-4-butyloxycarbonylphenyl \ -3- (2-chloro-4-tetradecyloxycarbonylanilino) derivatives

(42) 1- (2-Chloro-3,5-dimethoxycarbonylphenyl) -3- (2-methoxy-4-dodecyloxycarbonylanilino) derivatives

(43) 1- (2,6-Dichloro-4-ethoxycarbonylphenyl) -3- (2-chloro-4- (2- (2,4-di-tert-pentylphenoxy) ethoxycarbonyl) aniline) derivatives

(44) 1- (2,6-Dichloro-4-propyloxycarbonylphenyl) -3- (2-chloro-5- (2- (4-hydroxy-3-tert-butylphenoxy) tetradecyloxycarbonyl) anilino) derivatives

(45) 1- (2,6-Dichloro-4-ethoxycarbonylphenyl) -3- (2-chloro-5-tetradecyloxycarbonylanilino) -4- (2-naphthylazo) derivatives

(46) 1- (2,6-dichloro-4-cyclohexyloxycarbonylphenyl) -3- (2-chloro-4-hexadecyloxycarbonylanilino) -4- (4-hydrbxy-3-methylphenylazo) derivatives.

The magenta couplers used in the context of the present invention can be prepared by processes known per se. Some preparation examples for the synthesis more representative Coupler examples are described in detail below. The other couplers described above can be prepared in the same manner.

Production example 1

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1 - (2.4 , 6-trichlorophenyl) -3- (2-chloro-5-te-t: radecyloxycarbonylanilino) -2-pyrazol-5-one (coupler (5))

(1) Synthesis of 1- (2,4,6-trichlorophenyl) -3- (2-chloro-5-methoxycarbonylanilino) -2-pyrazol-5-one:

Method a):

70 g of 1- (2,4,6-trichlorophenyl) -3-amino-2-pyrazol-5-one _# 46 g of 2-chloro-5-methoxycarbonylaniline and 50 g of phosphoric acid were stirred under nitrogen for 2 hours, the temperature of the system was kept at 170-190 C. The reaction mixture was extracted with hot acetonitrile and then cooled. A small amount of colored by-product was immediately separated. The filtrate from this separation of the by-product was left to stand, the desired pyrazolone settling out. The melting point of the colorless crystals obtained after recrystallization of the crude product from acetonitrile was 22 ° C.

Method b):

20.4 g of ethyl-S-ethoxy-S-ethyl mercapto acrylate, which was obtained by the method of G. Barnikow et al. Chem. Ber. 100 (1967), 1428 , and 18.6 g of 2-chloro-5-methoxycarbonylaniline were stirred with heating at 140-150 ° C. for 2 hours. Without isolating and purifying the ethyl 3- (2-chloro-5-methoxycarbonylanilino) -3-ethoxy-acrylate obtained in this way, 16 g of 2,4,6-trichlorophenylhydrazine and 100 ml of acetic acid were added to the reaction mixture given. The resulting mixture was refluxed for 2 hours. After the acetic acid had been distilled off from the reaction mixture, 100 ml of acetonitrile were added. The mixture was then left to stand, whereby the desired pyrazolone crystallized out. The product showed a melting point of

40 9 8 2 1 / 1G-6S

219-220 ° C.

Method c):

52 g of ethyl 3,3-diethoxy-acrylate, which was prepared by the method of SA Glickman et al., J. Am. Chem. Soc. 67 (1945) _f 1017 , and 55 g of 2-chloro-5-methoxycartonylaniline were heated and stirred at 130-140 ° C. for 5 hours. Without isolating or purifying the ethyl-Si ^ -chloro-S-methoxycarbonylanilino) -3-ethoxy-acrylate obtained in this way, 60 g of 2,4,6-trichlorophenylhydrazine and 400 ml of acetic acid were added to the reaction mixture. The mixture was then refluxed for 2 hours. After the acetic acid had been distilled off from the reaction mixture, 300 ml of acetonitrile were added and the mixture was allowed to stand, the desired pyrazolone separating out. The melting point of the product thus obtained was 220 C.

Method d):

The synthesis corresponds to the procedure described in US Pat. No. 3,152,896:.

By reacting 2-chloro-5-methoxycarbonylaniline with thiophosgene, 2-chloro-5-methoxycarbonyl isothiocyanate with a melting point of 60-61 ° C. was produced. The thiocyanate thus obtained was purified by the method of GM Dyson et al. J. Chem. Soc. 129 (1926), 3041 added to a solution obtained by reacting equivalent amounts of ethyl acetoacetate with sodium methylate in an alcohol, and then heated. The reaction mixture was then reacted with an excess of methyl iodide. After heating for one hour, the excess methyl iodide was removed under reduced pressure. An equivalent amount was then used

409821/1065

of 2,4,6-trichlorophenylhydrazine added and so resulting mixture heated for 20 hours. The reaction mixture was then poured into water, extracted with benzene, dried with anhydrous sodium sulfate and then constricted. The residue obtained was dissolved in an alcoholic solution of sodium methylate and 30 min warmed up for a long time. After cooling, the reaction mixture became poured into water and acidified with acetic acid. An oily product separated out which was collected and incorporated into Acetonitrile was dissolved. After the solution was left to stand, colorless crystals separated out, which have a melting point of 220 C. The product obtained was treated with a known sample of 1- (2,4,6-trichlorophenyl) -3- (2-chloro-5-methoxycarbonylanilino) -2-pyrazol-5-one, which had been obtained by method a), mixed and subjected to a melting point determination. There was no lowering of the melting point observed.

Method e):

The synthesis described here corresponds to the process according to US Pat. No. 3,615,506:

By mixing 15.4 g of l- (2,4,6-trichlorophenyl} -3-ethoxy-2-pyrazol-5-one Using 9.3 g of 2-chloro-5-methoxycarbonylaniline and heating to 140 ° C., a homogeneous melt was produced. The melt obtained in this way was admixed with 18 g of anhydrous p-toluenesulfanic acid. The thus obtained The reaction mixture was stirred for one hour under reduced pressure at 14O-15O C with removal of the formed ethanol implemented. After the reaction had ended, the mixture was allowed to cool to 100.degree. Then was acetonitrile is added to the solution. The resulting mixture was cooled with ice. The precipitated crystals

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were separated from the cold mixture by filtration and then recrystallized from acetonitrile. The thus-obtained colorless crystals had a melting point of 219-220 ⁰ C. The crystals were ümkristallisierten with 1- (2,4,6-trichlorophenyl) -3- (2-chloro-5-methoxycarbonylanilino) -2-pyrazol-5- on, which had been obtained by method a), mixed and subjected to a melting point determination. No lowering of the melting point was observed. In addition, completely identical IR absorption spectra were obtained from both samples.

(2) Synthesis of the coupler (5):

44.7 g of 1- (2,4,6-trichlorophenyl) -3- (2-chloro-5-methoxycarbonylanilino) -2-pyrazol-5-one prepared by one of the processes a) to e) described above were reacted with 28.0 g of 1-tetradecanol in the presence of 3.0 g of butyl titanate as a catalyst by the method described in Japanese Patent Laid-Open No. 5582/67, whereby an ester interchange reaction occurred. The reaction product obtained in this way was recrystallized from ethanol and gave the colorless crystals of the desired coupler, namely the compound 1- (2,4,6-trichlorophenyl) -3- (2-chloro-5-tetradecyloxycarbonylanilino) -2-pyrazole-5- on. The melting point of the coupler obtained in this way was 95 98 ⁰ C.

Production example 2

1- (2,4,6-Trichlorophenyl) -3- (2-methoxy-5-tetradecyloxycarbonylanilino) -2-pyrazol-5-one (coupler (4))

Instead of the 2-chloro-5-methoxycarbonylaniline, which is im Method d) of Synthesis Example 1- (1) described above was used to obtain 2-methoxy-5-methoxycarbonylaniline implemented under the same conditions. After recrystallization

• i G 9 8 2 1/1 0 6 5

Sizing the product thus obtained from acetonitrile, colorless crystals of 1- (2,4,6-triochlorophenyl) -3- (2-methoxy-5-methoxycarbonylanilino) -2-pyrazol-5-one were obtained. The methyl ester obtained was reacted with 1-tetradecanol as described in Preparation Example 1- (2). The product obtained in this way was recrystallized from methanol, the colorless crystals of the coupler (4) having a melting point of HO-111 ^° C. being obtained.

Production example 3

1- (2,4,6-Trichlorophenyl) -3- (2-chloro-5- (2- (2,4-di-tert-pentylphenoxy) ethoxycarbonyl) anilino) -2-pyrazoJ ^ j-one (Coupler (8))

1- (2,4,6-trichlorophenyl) -3- (2-chloro-5-methoxycarbonylanilino) -2-pyrazol-5-one, that according to one of the processes a) to e) of the above preparation example 1- (1) had been obtained, was with 1.2 equivalents of 2,4-di-tert-pentylphenoxyethanol (Boiling point at 1 mmHg: 125 C) in the presence of butyl titanate as a catalyst the conditions described in Preparation Example l- (2) implemented. The product obtained was made from ethanol recrystallized and gave the colorless crystals of the coupler (8), which had a melting point of 110-111C had.

Production example 4

1- (2,4,6-Trichlorophenyl) -3- (2-chloro-5-hexadecyloxycarbonylanilino) -4- (4-irtethoxyphenylazo) -2-pyrazol-5-one (Coupler (2O))

An aqueous solution containing 1.2 equivalents was added to a pyridine solution of 1- (2,4,6-trichlorophenyl) -3- ( 2- chloro-5-hexadecyloxycarbonylanilino) -2-pyrazol-5-one

409821/10 6 pp

containing diazotized p-anisidine, added at a temperature of 5 ° C or below and stirred for 30 minutes. The gradually separated out from the reaction mixture yellow crystals were separated by filtration, washed with water and recrystallized from ethanol, v / obei the desired coupler (20) having a melting point of 125-127 ⁰ C was obtained.

The magenta couplers according to the invention have a high Coupling reactivity and sufficient solubility in organic solvents. Those using them produced color photographic materials extremely good photographic properties, for example a high sensitivity and a good one optical gradation. In addition, the magenta couplers used for the silver halide photographic emulsions are required according to the invention can be easily manufactured in a simple manner. Additionally the color photographic images obtained after the processing of the materials are extraordinary favorable spectral absorption characteristics and sufficient speed for color reproduction on. Furthermore, when they are stored for long periods of time, they are under extremely difficult conditions extremely well storable. Further characteristic features of the invention are detailed below further described.

The 3-anilino-2- pyrazol-5-one couplers used in the context of the invention of general formula (I) differ structurally from those in GB-PS 956 261, US-PS 3 419 391 and the Japanese Äuslegeschrift 19032/71 described couplers insofar as those described here Couplers of the formula (I) have an alkoxycaxbonyl group on the anilino group, while the known

405821/1065

Couplers carry an acylamino group on the anilino group. The couplers with an alkoxycarbonyl group used in the context of the present invention produce color images having better spectral absorption characteristics than those couplers containing an acylaminoanilino group. With the couplers used in the present invention, azomethine colors are formed which cause undesirable absorption of the red and blue light to a lesser extent and in this way in the processing of color photographic Material also red and blue shades bright and razor sharp and without color impairment can reproduce. Furthermore, the 2-pyrazol-5-one couplers used in the context of the invention, the one Alkoxycarbonyl group, more easily than the acylamino group-containing couplers in organic solvents soluble.

If you have the. couplers used in the invention with the 3-acylamino and the 3-ureido-2-pyrazol-5-one couplers prior art, which have been used as the best known magenta couplers, compares, it can thus be established that the couplers according to the invention lead to images whose spectral absorption characteristics clearly match the known characteristics are superior in that the couplers have a higher reactivity with the oxidation products of the primary aromatic Amine developers have that the color images obtained are more heat-resistant and that to stabilize these color images In particular, no special aftertreatment is required for temperature stabilization. These Improvements and advantages achieved with the emulsions according to the invention are referenced below described in more detail by experiments.

(i) The spectral absorption characteristics of the Parb carriers:

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The spectral absorption characteristics of azomethine dyes, which form the color images were examined in ethyl acetate solutions. The for these comparative experiments The dyes used were the oxidation coupling products of the couplers listed below with 4- (N-ethyl-N- (2-methanesulfonamidoethyl) -amino) -2-me thylani1in:

Coupler (5) according to the invention:

1- (2,4,6-Trichlorophenyl) -3- (2-chloro-5-tetradecyloxycarbonylanilino) -2-pyrazol-5-one

Prior art coupler (A) (containing a 3-acylaminoanilino group):

1- (2,4,6-Trichlorophenyl) -3- (2-chloro-4- (4- (2,4-di-tert-pentylphenoxy) -butylamido) -anilino) -2-pyrazol-5-one

(Coupler B) according to the prior art (containing a 3-acylamino group):

1- (2,4,6-Trichlorophenyl) -3- (3- (2- (2,4-di-tert-pentylphehoxy) -acetamido) -benzamido) -2-pyrazol-5-one.

The spectral absorption curves of each of these dyes were obtained in such a manner that the density at the The wavelength of the maximum absorption (1st absorption) was set to 1.0. From this spectral absorption curve a second absorption density (i) in the range of blue light, a density (II) at a 60 nm longer Wavelength as the first absorption wavelength and that wavelength spacing (III) is determined at which the density was 0.5. This is the spectral absorption

409321/1065

0.137 O.121 65 0.147 0.165 70 0.231 0.237 82

characterizing data (i) to (III) are in the Table I below compiled.

Table I. Absorption characteristics of the dyes formed

Coupler (I) (il) (Hl)

Coupler (5) coupler (A) coupler (B)

The results, compiled in Table I, show that the spectral absorption curve of the using the color image obtained according to the invention of the magenta coupler is cut off sharply on the long-wave side is and still shows hardly any undesirable secondary absorption. With those used in the context of the invention Excellent magenta couplers can be obtained.

With regard to conventional magenta couplers, in particular to those magenta couplers that have a 3-acylamino or 3-ureido substituent on the 2-pyrazol-5-one core contain, it must be noted that the color images produced with their use have a distinctly in show the long-wave range expiring spectral absorption curve as soon as lower amounts of non-volatile organic solvent with a high boiling point are incorporated into the emulsion. As soon as large quantities such a non-volatile organic solvent With a high boiling point are incorporated into the emulsions, this flat drop is somewhat in the long-wave range

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~ 27 -

softened..In another point of view, so the desired forces Improvement or the lower, not to be undercut Limit with regard to the spectral absorption characteristics when using the known magenta couplers for Use of relatively large amounts of the solvents mentioned. In contrast to this, the spectral absorption behavior is that with the 3-anilino-2-pyrazol-5-one couplers according to the invention produced color images practically independent of the amount of the couplers used Solvent and outstanding even when the amount of solvent is noticeably reduced. The in the frame According to the invention, the couplers used for the preparation of the emulsions thus enable, above all, a reduction the layer thickness of the individual emulsion layers, namely to values in the range of 1-8 / um, preferably 3-6 / µm.

(II) Solubility of the couplers in organic solvents:

In the case of oil-soluble couplers, the procedure is advantageous so that you first dissolve this in organic solvents and then this solution in an aqueous medium dispersed. This dispersion is then the added to photographic emulsions. It is for this it is desirable that the couplers are readily soluble in the organic solvents. The couplers (4) and (5) according to the invention were with the couplers (A), {C), (D) and (E) after. Prior art compared that have an acylaminoanilino group. The Solubility of these couplers in ethyl acetate at 25 ° C. the Results are summarized in Table II. The following prior art couplers were used:

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Coupler (Ä):

as stated above.

Coupler (C):

1- (2,4,6-Trichlorophenyi) -3- (2-methoxy-4- (2- (2,4-di-tert-pentylphenoxy} -butylamido) anilino) -2-pyrazol-5-one

Coupler (D):

1- (2,4,6 ~ Trichlorophenyl) -3- (2-chloro-5- (2- (2,4-di-tert-pentylphenoxy) -butylamido) -anilino) -2-pyrazol-5-one

Coupler (E):

1- (2,4,6-Trichlorophenyl) -3- (2.-ChIOr-S- (4- (2,4-di-tert-pentylphenoxy) -butylamido) -anilino) -2-pyra2ol-5-one

Dialkylphenoxyalkylcarbony groups have been used as acyl groups of these couplers which are the most common ballast groups for oil soluble couplers.

Table II Liability of the couplers in ethyl acetate

Coupler 3-substituent of the melt solubility

2-pyrazol-5-ons point (C) (g / lOO g solution)

Invention:

Coupler (4) 2-chloro-5-alkoxy-110-111

carbonyl

Coupler (5) "95-98 40 and above

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Table II (continued)

State of the art:

Coupler (A) 2-chloro-4-
acylamino-
anilino 184-187 4th Coupler (C) Il 250-253 1 and
fewer Coupler (D) 2-chloro-5-
acylaminoani-
lino 2O3-2O5 4.5 Coupler (E) Il 166-168 1

The results shown in Table II above indicate that the 2-pyrazol-5-one couplers which according to the invention a 3-alkoxycarbonylanilino group have lower melting points and higher solubility as the known couplers having a 3-acylaminoanilino group to have. The couplers (4) and (5) according to the invention show when dissolved in large amounts of Ethyl acetate at 25 C has a solution heat absorption of 7.37 and 7.84 kcal / mol. These heats of solution and the low ones Melting points of the couplers according to the invention mean that these couplers can also be used at low temperatures have sufficient solubility to make the to be able to solve the problem underlying the invention. In practice, this means that the couplers according to of the invention are readily dispersible, requiring only small amounts of coupler solvent, which leads to the fact that, when using non-volatile organic solvents, the solvent applied to the films The residual amount of solvent remaining in emulsions can be extremely small. As a result, the required Minimum layer thickness of the emulsion layers can be significantly reduced, so that in the layers

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any light scattering that occurs is reduced and thus sharper color images can be obtained. In addition, the Couplers according to the invention have the beneficial property that they are very difficult in the emulsions or in the Crystallize applied or dried layers.

Cm) The oxidative coupling reactivity between the couplers and the developers:

The couplers (5) according to the invention and (A) and (B) according to the prior art were oxidative coupling with 4- (N-ethyl-N- (2-methanesulfonamidoethyl) amino) -2-methylaniline in the presence of a Cyan coupler, namely in the presence of 2- (2- (2,4-di-tert-pentylphenoxy) acetamido) 4,6-dichloro-5-methylphenol, subjected. The relative coupling speed was calculated for each of the cases. This relative coupling speed was determined as follows: The coupling reactivity of a coupler is determined relatively in such a way that one measures the dye content in the color images, which develop by adding two different types of couplers M and N, which develop clearly distinguishable and separate colors an emulsion. These two couplers are added as a mixture to the emulsion. The color photographic material thus obtained is then subjected to color development. If the coupler M has an image with a maximum density of (p) and a

JXl HIcI-X.

mean density of D and coupler N has a maximum image density of (D _M ) and an average density of D, the ratio of the reactivities of both couplers is determined by the following formula:

log 1-Tβ-75

^v h max ^K in

fFi 0 65

In practice, a series of values log 1 - ——-— -—

-. Max

for several pairs of values D _M and EL, which can be obtained from the color images * These color images are produced in such a way that emulsions containing the mixed couplers are subjected to color development after different exposure. The fourth pairs obtained are correspondingly transferred into a Cartesian coordinate system, from which the slope or the coupling reactivity ratio Rjy / Xj can then be determined.

The relative coupling speeds determined in this way are compiled in the table !!! ".

Tabel III •
3-substituent des
Pyrazolones Relative clutch
speed Relative Alkoxycarbonylaniiino
Acylaminoanilino
Acylamino 0.78
0.5.6
0.45 Coupler "Coupling speed Coupler
Coupler
Coupler (5)
(A)
(B)

From the data compiled in Table III it can be seen that the coupler (5) according to the invention ' reacts faster with the oxidation product of the color developer used than with the known couplers (A) or * (B). Accordingly, the color photographic materials according to the invention have a high sensitivity to green

: 409821 / 106-5

a high magenta density and a good optical color gradation and thus lead to exceptionally good color images.

(IV) The stability of the color images:

Using the new couplers according to the invention produced magenta color images have a number of typical advantages, such as these, that they are against the action of heat and moisture are extremely stable. They also have a high level of lightfastness. It is known that color images, made with conventional magenta couplers of the 2-pyrazol-5-one type, the couplers being a 3-acylamino- or 3-ureido group, have only very poor heat resistance. This The effect is presumably due to the fact that the couplers still remaining in the layer with the couplers formed Dyes continue to react to form colorless products. To avoid such degradation, those after State of the art color images obtained have been post-treated with special agents, for example with formaldehyde.

The color images obtained with couplers according to the invention do not require this type of post-treatment and have an extremely good color fastness. With regard to the heat resistance of the images thus formed, Example 2 described below Comparison data compiled. The color photographic images produced with emulsions according to the invention do not require any additional chemical treatment to improve heat resistance, in particular no post-treatment with formaldehyde. The development process of the exposed films can therefore

40982 1 / 1G65

can be substantially simplified overall, thereby achieving one of the most important practical advantages of the invention will.

The new couplers can be incorporated into the emulsions according to the invention in various ways. Some Examples are described in more detail below:

(a) A coupler is dissolved in an organic solvent which in turn is sparingly soluble in water and has a high boiling point, for example from 200 C or above, optionally a boiling point of up to 250 C at 1 mmHg. The coupler solution thus obtained becomes emulsified and dispersed in an aqueous medium. The dispersion thus obtained then becomes the photographic one Emulsion added. Suitable organic solvents for this process are, for example, carboxylic acid esters, such as alkyl or aryl esters of phthalic acid or citric acid, for example dibutyl phthalate, phosphoric acid esters, such as alkyl or aryl esters of phosphoric acid, for example tricresyl phosphate, amides, such as alkyl or aryl amides of carboxylic acids, for example Ν, Ν-diethylcaproamide, ethers, such as alkyl or arylphenyl ethers, alkyl or Arylphenols, for example p-n-nonylphenol, 2-methyl-4-n-octylphenol, Glycerol esters such as glycerides, and other. The listed compound classes and examples are only more suitable for emphasis Understand solvents with a high boiling point, the high boiling point being an important functional property is.

(b) A coupler is dissolved in a solvent which is relatively sparingly soluble in water and has a low solubility Has boiling point, for example in the range from 35-160 ° C., preferably in the range from 60-130 ° C. The thus obtained

409821/1065

Coupler solution is emulsified and dispersed in an aqueous medium and then the photographic emulsion added. The organic solvent is removed during the manufacture of the photographic material. . Suitable representatives for such solvents are, for example, ethyl acetate, cyclohexanone or ß-butylethoxyethyl acetate.

(b) A coupler is dissolved in an organic solvent which is readily miscible with water. The received Coupler solution is added to the photographic emulsion, wherein the coupler is distributed in the emulsion in the form of fine colloidal particles. The solvent used can be removed during manufacture of the photographic material, but can also be in the emulsion layer remain. As examples of suitable organic solvents that are easily miscible with water and can be used for this process, the following may be mentioned: dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, glycerine or tetrahydrofuran. Suitable Solvents for processes (a) through (c) are disclosed in U.S. Patents 2,322,027, 2,835,579, 3,253,921, and 3,574,627 disclosed.

Depending on the nature of the solubility of the couplers, those described in the above processes (a), (b) and (c) can be used Solvents can also be used as a mixture, whereby the dispersion conditions for the couplers can be improved with a suitable combination.

Furthermore, the coupler can also be added by a method similar to the method of addition in the aqueous System is similar. That in the procedure described above

(c) the solvent used is mixed with water.

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A base such as sodium hydroxide is added to this mixture. In the combined solvent thus obtained, the coupler is dissolved to form a substantially aqueous solution. The aqueous coupler solution thus obtained is added to the photographic emulsion. Couplers particularly suitable for this process are those which contain a group which promotes solubility in water, for example a carboxyl group, in any of the radicals R ₁ , R 2, X, -Y or Z of the above-mentioned general formula (I).

For the manufacture of silver halide color photographic materials according to the invention using the new couplers described herein, the under the general formula (I) falling coupler, alone or in Form of coupler mixtures can be used. The couplers according to the invention can also be known per se Couplers not falling under the formula (I) are used, for example with the magenta color couplers which in U.S. Patents 2,600,788, 2,725,292, 2,908,573, 2,983,608, 3,062,653, 3,311,476, 3,419,391, 3,468,666, 3,519,429, 3,558,319 or 3,582,322. They can also get in touch with others using the method of Magenta coupler added to an aqueous solution of the same emulsion be used. Furthermore, the magenta couplers falling under the general formula (I) can be combined are used with other cyan or yellow couplers in the same emulsion layer, as in Japanese 391/65 described way the color fidelity of the color photographic Increase playback.

The color photographic emulsions with one or more Couplers according to the invention are on a per se known photographic support, for example on a film or on baryta paper. With the emulsions

409821/1065

According to the invention, the most varied of types can be used color photographic material, such as color positive films, color negative films, color reversal films, color photographic positive papers and others more.

In the silver halide photographic emulsions described above are silver halides, such as silver chloride, silver bromide, silver iodide, Silver bromide iodide, silver iodide chloride or silver iodobromide chloride, as so-called halogen-converted silver halide grains as described for example in US-PS 3,622,318 and GB-PS 635,841 are. These photographic emulsions can optionally contain the natural sensitizers present in gelatin contain, and may also contain sulfur sensitizers, Contain noble metal salts and reduction sensitizers, such as those described in US Pat. No. 1,574,944, 2 399 O83, 2 410 689, 2 487 850, 2 521 925, 2 54O 085, 2,642,361 and 2,983,6O9. The emulsions may further contain optical sensitizers to increase the specific color sensitivity, as they do for example in U.S. Patents 2,519,001, 2,666,761, 2,739 and 3,481,742. You can also contain photo additives known per se, for example Anti-blooming or fogging agents, stabilizers, dyes that make the photographic Make material radiation-proof. Anti-staining agents, coating aids, polymers, plasticizers for the gelatine or hardener for the gelatine. Appropriate anti-obfuscation agents or stabilizers, which can be used are disclosed in U.S. Patents 2,728,663 to 2,728,667, 2,131,038, 2,377,375, 2,394,198, 2 403 927, 2 691 588, 2 708 162 and 3 163 536. Suitable agents that suppress staining are

409821/1065

in U.S. Patents 2,360,290, 2,403,721, 2,704,713, 2,732,300, and 2,735,765. Suitable anti-blooming agents are described in U.S. Patent 3,615,546. Suitable plasticizers for gelatin can be found in U.S. Patents 2,286,215, 2,327,808, 2,322,085, 2,768,154, 2,808,331, 2,904,434 and 2 94,854. Suitable gelatin hardeners are U.S. Patents 3,232,763 _t 3 232 764, 3 288 775, 3 635 718,

2 732 316, 3 0Ϊ7 280, 2 725 294, 2 725 295, 2 983 611,

3 103 437, 2 586 168, 3 543 292, 3 321 313, 3 186 848,

3 490 911 and 3 671 256 can be found. Suitable coating aids can be found in the following U.S. Patents 3,415,649, 2,992,108, 3,068,101, 3,133,816, 2,831,766, and 3,666,478. Suitable polymers which can be used for the layers are described in US Pat. Nos. 2,290,289, 2,772,163, 2,852,382 and 3,619,195.

The color photographic materials advantageously contain according to the invention together with the 3-anilino-2-pyrazol ~ 5-one compound according to the formula (T) a p-substituted phenol. This addition can increase the stability of color photographs can be enhanced. Typical representatives of such p-substituted phenols, in particular are suitable for stabilizing the color photographic recordings according to the invention are the hydroquinones, as described, for example, in the following U.S. Patents: 2,360,290, 2,418,613, 2,675,314, 3,701,179, 2,704,713,

2 728 659, 2 732 300, 2 735 765, 2 710 801 and 2 816 028. The gallic acid derivatives disclosed in U.S. Patents 3,457,079 and 3,069,262 can be used for the same purpose and in Japanese Patent Application Laid-Open No. 13496/68. The p-alkoxyphenols also serve the same purpose according to US-PS 2,735,765 and 36S8 909 and the p-oxyphenols according to US-PS 3,432,300, 3,573,050 and

3,574,627 and US patent application 213 54Ο / 1971.

409821/10

These compounds are non-coupling compounds of the general formula A-OH, in which A is a substituted phenyl radical, also a phenyl radical connected to a heterocyclic ring system in the 4-5 position to the OH group. In particular A is the residue of a hydroxyphenyl ether, a 6-hydroxychroman, a 5-hydroxycoumaran, a Hexahydrodibenzof uran-5 "ols and a 6, 6 '-dihydroxyspirochroman. Examples of such compounds are the following:

(1) 2, 2-dimethyl-4-methyl-6-hydroxy-7-octyl-chroman

(2) 2, 2-dimethyl-4-isopropyl-6-hydroxy-7-octyl-chroman

(3) 2-Methyl-2- (4,8-dimethyl) -nonyl-e-hydroxy -? - (or 8 -) - octyl-chroman

(4) 2- (N-Methyl-N-phenyl) -amino-3,3-dimethyl-5-hydroxycoumaran

(5) 2-methyl-2-hexadecyl-6-hydroxy-7-tert-butyl-chromane

(6) 2, 2-dimethyl-4-isopropyl ~ 5-methyl-6-hydroxy-7-methyloxy-ehroman

(7) 2,2,4,5-tetramethyl-6-hydroxy-7,8-diraethoxy-chromane

(8) 2-Methyl-2-hexadecyl-6-hydroxy-8-tert-butyl-chroran

(9) 2-Methyl-2- (4,8-dimethyl) -nonyl-5-methyl-6-hydroxy-7,8-dimethoxy-chromane

(10) 2-Methyl-2- (4,8-dimethyl) -nonyl-6-hydroxy-7-tert-butyl-chromane

(11) 2- (N-Methyl-N-phenyl) -amino-3,3-dimethyl-5-hydroxy-6-tert-butyl-benzofuran

(12) 2-Hydroxy-3-octyl-5a-methyl-8-isopropyl-5a _/ 6.7 _/ 8 _# 9 _/ 9a-hexahydrodibenzofuran

(13) 2-tert-octyl-4-dodecyloxyphenol

40982171065

(14) 2-tert-octyl-4-isobornyloxyphenol

(15) 2- (γ-carboxyethyl 1) -a-piperidino-3,3-dimethyl-5-hydroxy-.6-tert-butyl-coumaran

(16) 2- (N-methyl-N- (p-carboxymethyl /) ~ benzyl) -amino-3,3-dimethyl-5-hydroxy-6-tert-butyl-coumaran

(17) 2-HydrOxy-3-octyl-5a-methyl-8-isopropyl-5a, 6,7,8,9, 9a-hexahydrodibenzof uran

(18) 2- (N-methyl-N- (p-carboxymethyl) -benzyl) -amino-3,3-dimethyl-5-hydroxy-6-tert-octyl-coumaran

(19) 2-Hydroxy-5a- (N-methyl-N-phenyl) -amino-5a, 6,7,8,9, 9a-hexahydro-dibenzof uran -. "...."

(20) 2-Methyl-2- (4-methyl) -3-pentenyl-6-hydroxy-7-tertoctylchromane

(21) 2,2,5,7,8-pentamethyl-4-isopropyl-6-chromane

(22) α-tocopherol

(23) β-tocopherol

(24) γ-tocopherol

(25) tT-tocopherol

(26) 6,6'-dihydroxy-4,4,4 ', 4', 7,7'-hexamethyl-bis-2,2'-spirochroman .

(27) 6,6 ^{l-dihydroxy-7,7'-di-tert-butyl-4,4,4 I,} 4'-tetramethyl-bis-2,2'-spirochroman

(28) 6,6'-dihydroxy-7,7'-dimethoxy-4,4,4 ', 4.' -1etramethylbis-2,2'-spirochroman

Any known per se can be used as hydrophilic colloids and colloids used for the same purpose, e.g. gelatin, acylated gelatin (e.g. acetylated gelatin, gelatin modified with phthalic acid or gelatin modified with succinic acid), grafted

409821/1065

- 4O -

Gelatin (for example a graft polymer from a Vinyl monomers with gelatin), albumin, gum coumarabic, agar-agar, alginates, cellulose derivatives (for example Hydroxyethyl cellulose or carboxymethyl cellulose), polyvinylpyrrolidone, polyvinyl alcohol, a copolymer! Sat of alkyl acrylate and acrylic acid.

Examples of such hydrophilic colloids are described in the following US patents: 2,286,215, 2,322,085, 2,327,808, 2,541,474, 2,563,791, 2,768,154, 2,8Ο8,331, 2,831,767 and 2,852,382.

The hydrophilic colloid layers that make up the 3-anilino-2-pyrazol-5-one coupler According to the invention, in particular the gelatin layers, can be mixed with different Types of crosslinking agents can be cured such as those described in the following U.S. patents Crosslinking agents: 1 574 944, 2 399 083, 2 410 689, 2 487 850, 2 521 925, 2 540 085, 2 642 361 and 2 983 6Ο9. For example, for many layers according to the Invention inorganic compounds such as chromic acid, zirconium salts or aldehydes as crosslinking agents can be used, with the chlorofluoric acid and 2-phenoxy-3-chloro-maleic aldehyde acid described in Japanese Patent Application Laid-Open No. 1872/71 which can be used effectively in the context of the invention. In particular, im Within the scope of the invention, however, crosslinking agents which are not of the aldehyde type, for example Polyepoxy compounds according to the Japanese Auslegeschrift 7133/59, poly (1-aziridinyl) compounds according to Japanese patent application 879Ο / 62 and compounds with active halogen as described in US Pat. No. 3,362 and 3,325,287.

40982 1/1085

Photographic materials containing couplers according to the invention are treated according to conventional methods. After exposure, they are treated with a developer of the p-phenylenediamine type and then treated in the bleach-fix bath, giving the previously discussed color images with excellent spectral absorption characteristics and good transparency. Representative examples of developers suitable for developing the color photographic material according to the invention are as follows: 4- (N, N-diethyl) -aminoaniline, 4-N-ethyl-N- (2-methanesulfonamidoethyl) -amino-2 -methylaniline, 4-N-ethyl-N- (ß-hydroxyethyl) -amino-2-methylaniline or 4- (N, N-diethyl) -amino-2-methylaniline, as described for example in one of the following publications: J. Am. Chem. Soc. , Vol. 73, pp. 3100-3125 (1951), J. Phot. May be. Eng., Vol. 8, No. 3, pp. 125-137 (1964), CEKMees and TH James, The Theory of the Photographic Process, 3rd Edition, pp. 294-295 and U.S. Patents 2,592,364 and 2,193,015.

A number of preferred embodiments of the invention are described in detail below.

example 1

A solution obtained by heating and dissolving 5 g of the above-described coupler (4) according to the invention 4 ml of tricresyl phosphate and 15 ml of ethyl acetate were added at 60 ° C to 50 ml of an aqueous solution also heated to 60 C, the 5 g of gelatin and Contained 0.15 g of sodium dodecylbenzenesulfonate. The mixed solution was used to prepare a coupler dispersion in stirred in a homogenizer. The coupler dispersion thus obtained was mixed with 100 g of a photographic emulsion mixed, the 5.6 χ 1O ~ mol silver bromide chloride (55 mol%

; 409821/1065

Silver chloride) and 10 g gelatin. Furthermore, a three percent solution of triethylenephosphamide in acetone was added as a hardener. The pH of the thus obtained
Geraisches was set to 6.5. The obtained mass was placed on a substrate made of a cellulose triacetate film and dried. The thickness of the dried. Layer was 4.5 µm. The photographic film obtained in this way was exposed in a manner known per se and then subjected to the treatment listed below with the specified steps, a clean magenta image with a maximum absorption at 537 nm
was obtained. The following treatments were carried out:

Treatment levels:

1. Color development at 21 C for 14 min

2. Wash with water "30 s

3. First fixation "4 min

4. Washing with water "4 min

5. Bleach "8 min

6. Wash with water "4 rain

7. Second fixation "4 min

8. Washing with water "6 min

Color developer:

4- (N, N-diethyl) -amino-2-methylaniline hydrochloride

anhydrous sodium sulfite sodium carbonate (HO) potassium bromide
water

2.5 g

10 G 47 G 2 G on 1 1 (pH: 1O, 5)

Fixing bath:

Sodium sulfate hexahydrate anhydrous sodium sulfite

8O
5

g g

4Ö9821 / 1065

2357 Ί

- »43 -

Borax _: 6th G Glacial acetic acid. · 4th ml Potassium alum 7th G water on
(pH: 1 1
4.5) Bleach bath: Potash hexacyanoj: guessed (III) 100 G Potassium bromide 5 G Boric acid 10 G borax 5 G water on
(pH: 1 1
7.2)

Example 2

A solution that has been obtained by heating and dissolving 3.7 g of Coupler (5) described above according to the invention 0.3 g of 2, 5-di-tert-octylhydroquinone, 2,5 nil tricresyl phosphate and 10 ml ethyl acetate at 60 C. was added to 40 ml of a 60 ° C aqueous solution containing 5 g of gelatin and 0.10 g of sodium dodecylbenzenesulfonate. To prepare the coupler dispersion, the mixed solution was stirred in the homogenizer. The coupler dispersion obtained in this way was treated with lpo g of a photographic

—2

mixed graphic emulsion containing 4.7 χ 10 mol of silver bromide chloride (50 mol% silver chloride) and 9 g gelatin contained. Then 5 ml of a 3% solution were added of triethylenephosphamide in acetone added as a hardener. The mixture obtained was then adjusted to a pH of 7.0 and coated with a resin Paper applied and dried. The thickness of the dried Coating was 2.6 / um .:

40-982 1/106

Other color photographs were made in the same way Papers using the above-described couplers (7), (10), (13) and (14) according to the invention and with the Couplers (A) and (B) produced according to the prior art.

The color photographic papers thus prepared were subject to the gradual assessment and then in

treated in the manner described below: Treatment stages:

1. Color developer 30 ° C 4th min 2. Bleach fixation ir 2 Il 3. Via see with water Il 2 Il 4th stabilization Il 2 Il

Color developer:

Sodium metaborate sodium sulfite hydroxylamine sulfate Potassium bromide 6-nitrobenzimidazole nitrate sodium hydroxide Benzyl alcohol diethylene glycol

4- (N-ethyl-N- (2-methynsulfonamidoethyl)) - amino-2-methylaniline sesquisulfate

water
Bleach-fix bath:

25th G 2 G 2 G O, 5 g O, 02 g 4th G 15, 8 ml 20th ml 8th G on 1 1

Iron (III) ethylenediamine tetraacetate 45 g Ammonium thiocyanate 10 g

40 9821/1065

10 G 100 ml 5 G on 1 1

Sodium sulfite
Ammonium thiosulphate (60 %)

Tetrasodium ethylenediamine tetraacetate

water
Stabilizing bath (a):

Tartaric acid 10 g

Lead sulfate 10 g

Sodium metaborate 20 g

Water on 1. 1

Stabilizing bath (b):

Tartaric acid 10 g

Lead sulfate 10 g

Sodium metaborate 20 g

Formalin (40%) 10 ml

Water on 1 1

^{Each of these samples was exposed to a temperature of 0} ° C. for 4 hours, to a temperature of ^{60 °} C. for two weeks at a relative humidity of 75% and to the light of a fluorescent lamp for two weeks. The degree of density reduction (%) based on the initial density of the obtained magenta image was determined in each of the cases. The results obtained are shown in Table IV below.

AO9821 / 1065

., 46 - ■

Table IV Color fastness of the images to heat and light

(relative percentage reduction in density compared to the initial density)

Stabilization coupler 120 ° C, 4 h 60 ⁰ ₁ C 75% RH Leuchtstoffrungsbad initial density, lamp 2 WO, 2-wk 0.5 1.0 Chen Chen

Initial density Initial density 0.5 1.0. 1, O

(7). (a) 8th 3 UO). (a) 9 k (13) (a) 9 k (U) (a) 8th k (A) (a) 10 7th (A) (a) 67 (B) (b) 8th 7,

8 6 19

8 k 20

9 5 21 9 7 23

33 19 25

9 6 23

The data shown in Table IV show that the.

Couplers according to the invention (7,10,13,14) provide color images whose color stability is at least equal to Color fastness of coupler (A) according to the prior art and in contrast to coupler (B) according to the State of the art do not require formalin stabilization. In sum, those with the couplers according to the invention

409821/1065

The color images obtained have a color fastness that is effective against the effects of temperature and light is clearly superior to the resistance values of the color images obtained according to the prior art.

Example 3

A series of solutions were prepared by heating to 60 ° C. and dissolving, namely by dissolving (a) 4 g of the above-described coupler (5) according to the invention and (b) 8 ml, 5.6 ml, 3.2 ml , 2 ml, 0.8 ml and 0 ml of tricresyl phosphate (TGP) and (c) 8 ml, 11 ml, 13 ml, 15 ml, 16 ml and 17 ml of ethyl acetate. Any of the so made. Solutions were added to 40 ml of an aqueous solution, heated to 60 ° C., which contained 4 g of gelatin μηα 0.10 g of sodium dodecylbenzenesulfonate. Each of the 6 mixed solutions thus obtained was stirred in the homogenizer to prepare the coupler dispersions. Each of the coupler dispersions thus obtained was mixed with 100 g of a photographic emulsion which contained 5.0 × 10 −8 mol of silver bromide chloride (50% by weight of silver chloride) and 9 g of gelatin. A further 5 ml of a three percent solution of triethylenephosphamide in acetone were then added to the mixtures as a hardener. Finally, the pH of each of the samples was adjusted to 7.0. The mass thus obtained was coated on cellulose triacetate films as a substrate and dried. Further coupler dispersions were prepared in the same way, with '(a) 4.4 g of the coupler (B) according to the prior art - and (b). 8.8 ml, 6.16 ml, 3.52 ml, 2.2 ml, 0.88 ml and 0 ml tricresyl phosphate and, (c) 9 ml, 12 ml, 14 ml, 16 ml, 17 ml and 18 ml of ethyl acetate were added. Each of the six solutions thus obtained was mixed with 100 g of the above-described photographic emulsion and then painted on and dried. Each of the photographic films thus obtained was made with

409821/106 5

treated with the developer specified below for 12 minutes at ° C and then, as described in Example 1, fixed, bleached and re-fixed. The layers obtained in this way for the various magenta images of the main absorption maximum are compiled in Table V below. The color developer used had the following composition:

Sodium hexametaphosphate 2 g

anhydrous sodium sulfite 2 g

Benzyl alcohol 5 ml

Sodium carbonate (HpO) 27.5 g

Potassium bromide 0.5 g

Hydroxylamine sulfate 2.5 g

4- (N-ethyl-N - (- methylsulfonamido-

ethyl) -amino) -2-methylaniline-

sesquisulfate 2.5g

Table V

The ratio of tricresyl phosphate (ml) / coupler (q) and the wavelength (mn) of the maximum of the main absorption

TCP / coupler coupler (5) coupler (B)

2 539 5 ^ 6

I ₁ room 539 5cl

0.8 539 5kS

0.5 5k0 550

0.2 5 * fl '553

556

409821/1065

- '40 -

From the data shown in Table V it can be seen that that the coupler (5) according to the invention good color images with excellent. Provides transparency even when the amount of the non-volatile high boiling point solvent used is decreased, whereby the coupler (5) did not crystallize in either the dispersion or the coated film. The data shown can be taken from will suggest a reduction in the non-volatile solvent used for the couplers with high Boiling point for the coupler according to the invention hardly any noticeable change in the spectral absorption data of the color images obtained with them "occurs. This leads to the fact that when the emulsion layers are produced according to FIG Invention less solvent can be used, which is too noticeable for the same performance of the emulsion layer leads to thinner layers.

Example 4

A blue-sensitive silver bromide chloride emulsion was applied to a paper coated with polyethylene, the α-pivaloyl-α- (5,5-dimethyl-3-hydantoinyl) -2-chloro-5- (2- (2,4-di-tert-pentylphenoxy) butylamido) acetoanilide contained. On this first layer, which was 3.0 / µm thick, a second layer consisting of gelatin with a thickness of 1.5 μm was then applied.

While heating to 60 ° C., a solution of the following composition was prepared: 3.7 g of that described above Coupler (5) according to the invention, 0.3 g of 2,5-di-tertoctylhydroquinone, 0.3 g 6,6'-dihydroxy-7,7'-dimethoxy-4,4,4 ', 4'-tetramethyl-bis-2,2'-spirochroman, 5.5 ml tricresyl phosphate and 12 ml ethyl acetate. This solution was added to 40 ml of an aqueous solution heated to 60 ° C., the 4 g of gelatin and 0.10 g of sodium dodecylbenzene sulfonate contained. To form the coupler dispersion was

409821/1065

the resulting mixed solution was stirred in a homogenizer. The coupler dispersion thus obtained was with 100 g of a mixed green-sensitive photographic emulsion, the 4.7 χ 10 mol S over bromide chlorid (50 mol% silver chloride) and contained 9 g of gelatin. The emulsion was then 5 ml of a three percent solution of Triethylenephosphamide in acetone added as a hardener. The pH of the resulting mixture was adjusted to 7.0. the thus obtained coating material was used as a third layer applied to the two layers described above, in such a way that the dried layer is a Thickness of 3.5 / µm. On this layer in turn was a fourth layer applied in a thickness of 1.5 μm, those from gelatin and 2- (5'-chlorobenzotriazol-2-yl) -4-methyl-6-tert-butylphenol and 2- (benzotriazol-2-yl) -4-tert-butylphenol duration. A red-sensitive emulsion was applied to this fourth layer as the fifth layer who have favourited 2- (2- (2,4-di-tert-pentylphenoxy) -butylamido) -4,6-dichloro-5-methyl-phenol contained. The thickness of the red-sensitive layer was 2.5 µm. On top of this red-sensitive layer, a Gelatin layer applied with a thickness of 1 yum, whereby a paper for color photographic printing was obtained (sample a).

Instead of the aforementioned coupler (5), 4, Og of a known coupler used as a magenta coupler, namely 4.0 g of the compound 1- (2,4,6-trichlorophenyl) -3- (3- (2- (2,4-di-tert-pentylphenoxy) -butylamido) - benzamid) -2-pyrazol-5-one. Otherwise, the procedure was as described for the preparation of sample a. That way it was another color printing paper (sample b) was obtained.

The samples thus obtained were exposed to a sensitometric exposure to green light, developed and

409821/1065

treated in the bleach-fix bath. The processes used correspond to the processes described in Example 2. Finally, the stabilization bath (a) also described was used for stabilization. Sample (a) produced a magenta color image with an absorption maximum at 539 nm, while sample b produced a magenta color image with an absorption maximum at 550 nm. The dye prints obtained in this way were stored for 4 weeks at 60 ° C. in a relative humidity of 75 % . Based on the initial density of 1.0, only a decrease in color intensity of 6% was observed for sample a according to the invention, while the color image of sample b according to the prior art under the same conditions was 17 % more relative Lost density.

The samples obtained in the manner described above were exposed through a transparent color negative and then subjected to the development described above. Compared with those using sample b The color positives obtained were the color positives of sample a according to the invention in the red area 'sharp and bright. These differences are due to the characteristics described above, in particular to that the spectral absorption of the magenta images obtained with the couplers according to the invention on the long-wave Page is sharply delimited, what for the coupler after State of the art is not the case.

Example 5 '.

On a film of cellulose triacetate as a substrate a first red-sensitive layer made of a silver bromide iodide emulsion applied, the l-hydroxy-2-tetradecylnaphthamide contained. On this first layer, the 5 / um was thick, a second layer was added to a thickness of

4 09821/1065

1.0 / tun from gelatin applied, the 2,5-di-tert-octylhydroquinone contained.

Furthermore, a solution with heating to 60 C and dissolving 15 g of the coupler described above (28) according to the invention, 2.0 g of the above-described coupler (20) according to the invention, 8 ml of tricresyl phosphate and 50 ml Obtain ethyl acetate. This solution was added to 150 ml of an aqueous solution heated to 60 ° C. which contained 15 g Gelatin and 0.4 g sodium dodecylbenzenesulfonate. The mixed solution thus obtained was used for preparation the coupler dispersion stirred in the homogenizer. These Coupler dispersion was mixed with 1 kg of a green-sensitive photographic emulsion which had 6 × 10 ~ mol Silver bromide iodide (6 mol% silver iodide) and 60 g gelatin contained. Then 5 ml of a three percent solution of 2-hydroxy-4,6-dichloro-S-triazine were used as hardener added as the sodium salt in acetone. The pH of the mixture thus obtained was adjusted to 7.0. That so The resulting mixture was applied as a third layer to the two layers previously prepared, namely in such that the thickness of the dried layer was 5.5 µm. On top of this third layer was a fourth layer applied containing gelatin and yellow colloidal silver and 2,5-di-tert-octylhydroquinone. The fat this layer was 1.5 µm. A blue-sensitive silver bromide iodide emulsion was also used as the fifth layer applied, the a- (p-Methoxybenzoyl) -a- (N-phthalimido) -2-chloro-5- (4- (2,4-di-tert-pentylphenoxy) -butylamido) -acetoanilide contained. On this layer the 5.0 aim thick Finally, an uppermost protective layer of gelatin was applied in a thickness of 1.0 μm. To this Thus, a color negative photographic material was obtained.

The film so produced was after exposure after

409821/1065

Process described below developed, with color negatives with high sensitivity, good color gradation and excellent image quality were obtained. It could also be shown that the blue density is independent the degree of green exposure remained practically constant and thus an adequate color correction could be obtained.

Treatment levels:

1. Color development 38 ° C 3: mi 2. To stop Il 1 Il 3. Wash with water Il 1 Il 4th bleaching M. 2 Il 5. Wash with water Il 1 Il 6th Fix Il 2 Il 7th Wash with water Il 1 Il 8th. Stabilize 11 1 Il

Color developer:

Sodium hydroxide 2 g

Sodium sulfite 2g

Potassium bromide. 0.4 g

Sodium chloride 1 g

Borax ■ 4g

Hydroxylamine sulfate 2 g

Ethylenediaminetetraacetic acid 2 g

4- (N-ethyl-N- (2-hydroxyethyl) -

amino) -2-methylaniline sesquisulfate 4 g

Water on 1

Stopper bath:

Sodium thiosulphate IO g

Ammonium thiosulphate (70%) 30 ml

40982 1/1065

Sodium acetate 5 g

Acetic acid. 30 ml

Potassium alum 15 g

Water, on 1

Bleach bath:

Sodium Iron (III) Ethylenediamine

tetraacetate dihydrate 100 g

. Potassium bromide 50 g

Ammonium nitrate 50 g

Boric acid 5 g

aqueous ammonia set axxi

pH 5.0

Water to 1 1 fixer bath:

Sodium thxosulfate

Sodium sulfite

borax

Glacial acetic acid

Potassium alum

water

Stabilizing bath:

Boric acid 5 g

Sodium citrate 5 g

Sodium metaborate (4H _? 0) 3 g

Potassium alum 15 g

Water - on 1 1

15Ο G 15th G 12th G 15th ml 2O G on 1 1

409821/1065

Example 6 '

By heating to 6O ⁰ C and dissolving 5 g of one of the couplers (2), (4), (5), (7), (8), (9), (10), (11), (13) , (14), (15), (16), (17), (18), (19), (20), (28) and (30) and 8 ml of tricresyl phosphate and 10 ml of ethyl acetate, a solution was prepared which, after emulsification and dispersion, would be mixed with a photographic solution and applied as a coating, dried, exposed and developed in the manner described in Example 1. Sharp color images with the following absorption maxima were obtained:

Coupler maximum absorption coupler maximum absorption

(mn) (nm)

(14) "543

(15) 543

(16) 543 (l?) 537

(18) 537

(19) 543

(20) 543 ^ S) 538 (30) 535

(2) 543 (4) 537 (5) 543 (7) • 537 (8th) 543 (9) 543 (10) 543 (11) • 543 (13) 543

40982 1/106 5

After taking note of the present description, those skilled in the art can use the exemplary embodiments described modify it further without departing from the scope of the invention.

40982 1 / 106-5

Claims (10)

Claims ... A silver halide photographic emulsion characterized by the presence of at least one non-diffusing one Magenta coupler of the 3-anilirP "2-pyrazol-5-one type, its phenyl ring in at least one of the two ortho positions with a halogen atom, alkyl, aryl, alkoxy, Aryloxy, alkylthio, arylthio, amino, amido, hydroxyl, Cyano or nitro and in at least one of the meta positions or the para position with an alkoxycarbonyl group is substituted. 2. Emulsion according to claim 1, characterized in that the 3-anilino-2-pyrazol-5-one coupler has the formula ff ^ \ - m - c CH -z- ^^ K \ c = o (D RpOC I ^ R ^X o ^ ₁ in which R is an aryl group or a heterocyclic group, R _{0 is} an alkyl group, X and Y are each an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group. group, an amino group, an amido group, a hydroxyl group, a cyano group, a nitro group or a halogen atom, and where Y can additionally be a hydrogen atom, and finally in which Z is a hydrogen atom or a radical which can be removed by the coupling. 3. Emulsion according to claim 2, characterized in that R, denotes a phenyl group which is at least in one 409821/1065 the ortho position is substituted with alkyl, alkoxy, alkylthio, cyano or halogen, that R ~ alkyl or one with alkoxy, aryloxy, acyloxy, alkoxycarbonyl, acylamino or. Carbamoyl-substituted alkyl means that X is halogen, an alkoxy group having 5 or fewer carbon atoms or an aryloxy group having 12 or fewer carbon atoms and Y is hydrogen. 4. Emulsion according to one of claims 2 or 3, characterized in that Z denotes hydrogen, halogen, thiocyano, acyloxy, aryloxy, arylazo, a heteroazo group, aryl thio or a heterothio group. 5. Emulsion according to one of claims 2 or 4, characterized in that X is methoxy, ethoxy, propoxy, fluorine, Is chlorine, bromine or a phenoxy group. 6. Emulsion according to one of claims 2 to 5, characterized characterized in that the radical R "OOC- in the 4-position the anilino group. 7. Emulsion according to one of claims 2 to 5, characterized. characterized in that the radical R ₂ OOG- is in the 5-position of the anilino group. 8. Emulsion according to claim 2, characterized in that the radical R-, the formula 40982 1/106 has, in.der U, halogen, alkyl, alkoxy, alkylthio, aryl, aryloxy, arylthio or cyano, in which U_ is hydrogen, halogen, alkyl, alkoxy, alkylthio, aryl, aryloxy, arylthio or cyano, and in U ^, U, and Ό " _ς each hydrogen, 'halogen, alkyl, alkoxy, alkylthio, aryl, aryloxy, arylthio, cyano, acylamino, carbamyl, ureido, sulfonamido., SuIf amyl, alkyl sulfonyl, arylsulfonyl, alkylcarbonyl, alkoxycarbonyl, Mean aralkoxycarbonyl, carboxyl or arylcarbonyl. 9. Emulsion according to one of claims 1 or 2, characterized in that the non-diffusing magenta coupler is one of the following: 1- (2,4,6-Trichlorophenyl) -3- (2-chloro-5-tetradodecyloxy ~ carbonylanilino) -2-pyrazol-5-one, 1- (2,4,6-trichlorophenyl) -3- (2-chloro-5- (3- (2,4-di-tertpentylphenoxy) -propoxycarbonyl), - anilino) -2-pyrazol-5-one, 1- (2,4,6-Trichlorophenyl) -3- (2-chloro-5- (2- (2,4-di-tert-pentylphenoxy) -butoxycarbonyl) -anilino) -2-pyrazol-5-one 1- (2,4,6-trichlorophenyl) -3- (2-chloro-5- (2- (3-pentadecylphenoxy) ethoxycarbonyl) anilino) -2-pyrazol-5-one, 1- (2,4,6-Trichlorophenyl) -3- (2-chloro-5- (2- (3-tert-butyl-4-hydroxyphenoxy) -tetradecyloxycarbonyl) -anilino) -2-pyrazol-5-one} or 1- (2,6-dichloro-4-methoxyphenyl) -3- (2-chloro-4-tetradecyloxycarbonylanilino) -2-pyrazole-S-ron. 10. Verv; end of the emulsions according to any one of claims 1 to 9 for the preparation of a carrier and at least a coating of existing photographic material. 409821/1065